Electrode for Energy Storage Device

ABSTRACT

An electrode for an electrochemical energy storage device formed from an electrostatic deposition process employs a composite particle including active material (AM) particle with adhered binder and optionally conductive particles formed with sufficient interaction forces between the individual ingredient particles to form an effective composite particle which can overcome particle separation during electrostatic charging, fluidization, and/or mechanical conveyance. Secondary binder particles undergo deagglomeration to form sub particles, which are adhered to the AM particles having a predetermined morphology. Smaller conductive particles, typically carbon black (CB) or similar carbon, are bound to the binder and adhere to the AM particles. The result is a composite particle adhered for withstanding separation forces imposed from electrostatic deposition onto a current collector. Application of a plurality of composite particles onto a conductive current collector in a uniform pattern and defined loading promotes robust energy density, power density, and cycle life for an electrochemical energy storage device.

CROSS-REFERENCE TO RELATED APPLICATION

The present application claims priority benefit to a U.S. provisionalapplication entitled “Electrode for Energy Storage Device,” which wasfiled on Jan. 31, 2022, and assigned Ser. No. 63/304,907. The entirecontent of the foregoing provisional application is incorporated hereinby reference.

BACKGROUND 1. Technical Field

The present disclosure is directed to electrochemical energy devices andassociated methods for manufacture. The disclosed electrochemical energydevices generally include electrode(s), wherein the electrode(s) includecoating layer(s) formed, at least in part, by depositing dry compositeparticles onto a conductive substrate by an electrostatic depositionprocess. The composite particles include an active material particle andbinder particles surrounding the active material particle, the binderparticles generally being formed from deagglomeration of binderagglomerates and adhering relative to the surface of the active materialparticle through particle-to-particle adherence forces.

2. Background Art

Electrochemical energy storage devices have electrodes that containcoating layers in communication with a conductive current collectorlayer, typically a copper or aluminum sheet. The coating layers mayinclude cathode active materials and anode active materials, and areoften combined with conductive materials and binder materials to form astructure that readily discharges and accepts charge (recharges)depending on an electric load or charging potential applied. Theformation of the electrochemical active materials, binder and conductiveparticles can vary according to applicable battery chemistry andproduction method.

Conventional approaches to battery manufacturing employ a solvent-basedapproach to forming an electrode. This typically involves a bindersolution or suspension for flowing or applying the electrochemicalactive material and conductive particles onto the conductive currentcollector foil. The conventional process generally involves solventsthat impose handling, ventilation, safety issues, and require a dryingtime for the liquid solvent to evaporate or fuse the ingredients in thecoated layer.

It is generally desirable to form a coating layer with an evendispersion of the electrochemical active materials, conductive particlesand binder in a density that promotes electrical communication betweenthe electrochemical active materials and current collectors to produce abattery with optimal energy density, power density and cycle life.Improvements in methods for application of coating layer(s) and in theelectrochemical active materials formed thereby are desired. These andother objectives are satisfied by the methods and devices of the presentdisclosure.

SUMMARY

An electrode for an electrochemical energy storage device formed from anelectrostatic deposition process is provided that employs a compositeparticle including electrochemical active material (or active material,“AM”) particles with adhered binder particles and optionally conductiveparticles formed with sufficient interactions between the individualingredient particles to form an effective composite particle which canovercome/resist particle separation forces during electrostatic chargingand fluidization in the electrostatic deposition process.

Commercially available binder materials or conductive materials aregenerally available in the form of agglomerates, often called secondaryparticles, that are formed by physical interaction of a plurality ofprimary particles. According to the present disclosure, binderagglomerates undergo deagglomeration to form sub particles, which areadhered to the AM particles having a predetermined and/or desirablemorphology. Of note, conductive agglomerates also form sub particlesthrough deagglomeration. A sub particle comprises one or more primaryparticles with a smaller size than the original agglomerate. In formingthe advantageous energy storage devices of the present disclosure, thebinder particle(s) and conductive particle(s) are incorporated in formof sub particle(s).

Typically, according to the present disclosure, carbon black (CB) orsimilar carbon is bound to the binder and adheres to the AM particlestogether with the binder. The result is composite particle(s) thatexhibit sufficient adhesion forces for withstanding separation forcesimposed during the electrostatic deposition process. In a typicalelectrostatic spray deposition (ESD) process, composite particles asdisclosed herein are aerated and fluidized by a gas flow and are carriedby the gas flow to deposit on a conductive current collector in auniform pattern and density. Alternate electrostatic depositionapproaches may also be used.

The deposited composite particle layer on the current collector may befurther densified according to the present disclosure to form anelectrode for a battery. The uniformity of the deposited compositeparticle layer is crucial to the performance of the resulting battery.The uniformity of the deposited composite particle layer entails, interalia, consistency of the chemical stoichiometry between the depositedlayer and the feedstock powder mixture, and consistency of chemicalstoichiometric and geometric consistency within the deposited layer.

There is substantial commercial interest in the battery industry toapply electrostatic deposition techniques to form a solvent-freeelectrode coating for Li-ion batteries. Solvent-free electrode coatingtechnologies are attractive because, inter alia, ESD techniques cansignificantly reduce energy consumption in the manufacturing process andsignificantly reduce the manufacturing cost of batteries. In principle,use of an electrostatic deposition technique allows a simpler and moreflexible electrode coating in the manufacture of energy storage devicesdue to direct deposition of composite electrode powders on metalliccurrent collector(s) through an electrostatic spray deposition process.

In conventional applications, electrostatic deposition techniques arewidely used in dry powder coating of conductive parts. In conventionalapplications of electrostatic deposition coating techniques, the coatinglayer quality, especially the coating layer uniformity, is directlyrelated to and dependent on properties of the particles included in thecoating powder. These properties include particle size, relativepermittivity, conductivity, density, morphology, and the like. Accordingto the present disclosure, the properties of the particles associatedwith the coating powder are selected such that an electrostaticdeposition coating formed with the disclosed composite particlesadvantageously promote/deliver a uniform electrode for batteryapplications.

Configurations herein are advantageously able to satisfy a need forreliable batteries across a range of end use applications, includingspecifically electric vehicles (EVs), which impose a substantial currentdraw to provide adequate vehicle performance. Unfortunately, and asnoted above, conventional approaches to battery manufacturing employ asolvent-based approach to forming an electrode. This typically involvesa binder solution or suspension for flowing or applying theelectrochemical active material and conductive particles onto theconductive current collector foil. The conventional process involvessolvents that impose handling, ventilation, safety issues, and require adrying time for the liquid solvent to evaporate or fuse the ingredientsin the coated layer. Accordingly, configurations herein substantiallyovercome the above shortcomings of solvent-based battery formulation byproviding an electrode including a composite particle for a dry powderapplication onto a conductive current collector using an electrostaticdeposition approach.

As disclosed herein, the desired morphology, or structure, of thecomposite particle(s) result from deagglomeration, mixing and adherencebetween ingredient particles to form an active material (AM) particlewith an adhered binder and optionally, conductive particles, in a formthat withstands the electrostatic deposition process. Once depositedonto a conductive current collector substrate, the disclosed AMparticles form/define precise loading and microstructure for highperformance batteries. Of note, “loading” is the unit coating layer massover a specified area, usually in mg/cm².

As disclosed herein, advantageous electrodes are formed by electrostaticdeposition of composite particles on a conductive current collector,thereby forming highly effective electrodes/electrochemical energystorage devices. The disclosed electrodes/electrochemical energy storagedevices generally include a plurality of composite particles adapted forelectrostatic deposition onto a conductive current collector substrate,wherein each composite particle includes one or more active materialparticles, binder particles surrounding the active material particle(s),and conductive particles adhered to the binder particles. The disclosedbinder particles are generally formed through deagglomeration of binderagglomerates to form sub particles. The binder particles adhere to asurface of an active material particle through interaction forces thatare sufficient to withstand the powder mixing process. The interactionsare also sufficient to overcome separation forces induced from theelectrostatic deposition process, which is ideal for maintaining astructure of the composite particle when formed onto the conductivecurrent collector substrate via the electrostatic deposition process.

The disclosed electrochemical energy storage devices and methods ofproduction thereof are highly advantageous in providing effective energystorage functionality without the need for a solvent-based manufacturingprocess.

Additional features, functions and benefits of the disclosedelectrochemical energy storage devices and associated manufacturingmethods will be apparent from the detailed description which follows,particularly when read in conjunction with the appended figures.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing and other features will be apparent from the followingdescription of particular embodiments disclosed herein, as illustratedin the accompanying drawings in which like reference characters refer tothe same parts throughout the different views.

The drawings are not necessarily to scale, emphasis instead being placedupon illustrating the principles of the invention.

FIG. 1 is a diagram of a composite particle as disclosed herein;

FIG. 2 shows a context for deploying the composite particle of FIG. 1 inan electrochemical energy storage device;

FIGS. 3A and 3B show example compositions of the composite particle ofFIG. 1 ;

FIG. 4 shows a progression through the formation of the compositeparticle of FIGS. 1-3B;

FIGS. 5A-5C are SEM images of mixed powders for Sample 1, Sample 3 andSample 4, respectively;

FIGS. 6A-6C are SEM images of larger areas of mixed powders for Sample1, Sample 3 and Sample 4, respectively;

FIGS. 7A-7C are EDS images (nickel mapping) of mixed powders for Sample1, Sample 3 and Sample 4, respectively;

FIGS. 8A-8C are EDS images (fluorine mapping) of mixed powders forSample 1, Sample 3 and Sample 4, respectively;

FIG. 9 is a plot showing bonding strength for electrodes prepared byelectrostatic spray deposition with powders with various mixing time andspeed, according to the present disclosure.

DETAILED DESCRIPTION

Depicted below is an example method and apparatus for forming anddeploying the composite particle in an electrochemical energy storagedevice, such as a rechargeable battery. Other particle depositionapproaches may be employed for engaging the composite particles with acurrent collector or other energy storage apparatus to store and releaseelectrical energy (electrons) for providing a current flow in acontrolled and efficient manner.

As described herein, the term “particle” generally denotes a granularquantity of a particulate substance adapted for mixing and interactingwith other particles. The morphology of particle can be spherical or anyother form. Examples referring to an individual particle are intended tobe illustrative of an occurrence or interaction affecting some or all ofthe particles in a granular quantity of particles, including powder andgranulated forms. It should be further noted that, in batteryterminology, “active charge material” is often referred to as“electrochemical active material” or “electrode active material.” Theelectrostatically deposited material thus deposited as disclosed hereinmay, depending on context, be referred to as a “coating layer.”

Agglomerations of particles often occur with bulk granular materials,including electrochemical active materials, binder materials, andconductive materials associated with manufacture of electrochemicalenergy storage devices according to the present disclosure. All of thesematerials take the form of particles, which may be in the form ofagglomerates, meaning multiple primary particles interacting throughrelatively weak forces broken through agitation and mixing. Commonnomenclature denotes the agglomerates as secondary particles and, onceagitated, broken into primary particles, or sub-particles. Whileprocesses and methods discussed herein generally function to formdiscrete primary particles from the sub particles of broken, stirred oragitated agglomerates, a particle as defined herein includes primaryparticles, secondary particles, sub particles of agglomerates, and anyinteraction or bonding between particles of a particular type. Stateddifferently, although clusters of primary particles, often calledsecondary particles or agglomerates, are generally expected todisassociate into smaller particles upon agitation, certainagglomerations may remain and nonetheless define a particle of therespective active material, binder, or conductive material, meaningparticles and/or any form of sub particles thereof. A particle maytherefore be broken into multiple sub particles, each of which is stilla particle, nonetheless. In addition, the force applied during theagitation process may be sufficient to pulverize the agglomeratedparticles.

FIG. 1 is a diagram of a composite particle as disclosed herein.Configurations herein apply a solvent-free (dry) electrostatic spraydeposition (ESD) coating technique for battery composite electrodemanufacturing with high uniformity. The present disclosure furtherenables composite powder mixing processes that produce suitablecomposite powder mixture for ESD electrode coating. Alternateapplications include any electrochemical storage device such as fuelcells, for example.

A battery has a cathode and an anode. In a typical Li-ion battery, thecathode and anode are based on composite electrode powder mixtures. Acomposite electrode powder mixture generally contains active electrodematerial particles (AM), binder material particles (Binder) andconductive material particles (CB). The active electrode materialsinclude cathode materials, such as lithium metal oxide based cathodematerials: NCM (Lithium Nickel Cobalt Manganese Oxide), LMO (LithiumManganese Oxide), NCA (Lithium Nickel Cobalt Aluminum Oxide), LCO(Lithium Cobalt Oxide) and lithium polyanion type cathode materials: LFP(Lithium Iron Phosphate), LiMn_(x)Fe_(1-x)PO₄, Li₂FeSiO₄, and anodematerials based on carbonaceous anode materials, graphite, Si, Si-basedcomposites, SiOx, lithium alloyable materials, or lithium transitionmetal oxide anode materials. In a typical sodium-ion battery, thecathode materials include sodium transition metal oxide, such asNa_(2/3)Fe_(1/2)Mn_(1/2)O₂, sodium polyanion materials, such Na₂MnSiO₄,Prussian Blue Analogues cathode materials, such as Na₂MnFe(CN)₆. Andanode materials include carbonaceous anode, sodium alloyable materials,sodium transition metal oxide or Prussian Blue Analogues anodematerials. The transition metal oxide-based cathode materials, such asNCM, are semi-conductors, with an electronic conductivity of 10⁻⁶ to10⁻⁷ S/cm.

Typical binder materials are polymeric materials, such as PVDF(polyvinylidene fluoride), PTFE (Polytetrafluoroethylene), PEO(Polyethylene oxide) or PMMA (Poly(methyl methacrylate)), SBR(Polystyrene butadiene rubber binder), CMC (Carboxymethyl cellulosebinder), or PAA (Polyacrylic acid), which are electrical insulators. Thebinder materials can also be polymer electrolytes, such as PEO/lithiumtriflate polymer electrolyte. Furthermore, the binder can be solid stateelectrolyte composites consisting of inorganic solid electrolytes andpolymeric binders, polymer electrolyte binders or organic binders, suchas Li₃InCl₆/PMMA composite, LLZO/polymer electrolyte composite.

Conductive materials may include carbon black (CB), carbon nanotubes, orgraphene, which are electrically conductive. In addition, somefunctional additives may be included in the composite electrode. Theseadditives may be, for example, silica, alumina, zirconium oxide or anycombination of them.

The true density of the cathode material is generally 4-5 g/cc for NCMand 3.6 g/cc for LFP. The true density of binder is typically in therange of 1-2 g/cc. The typical particle size for active materials is inthe range of 1-40 μm. The binder material typically has a primaryparticle size of 100-1000 nm and agglomerate size of 5-30 μm. Theconductive material typically has a primary particle size of 40-80 nm.The conductive current collectors are typically Al foil and Cu foil withor without prime layers to enhance adhesion between the coated layer andthe conductive substrate. Such an adhesion layer may be applied to theconductive substrate prior to deposition.

Referring to FIG. 1 , an electrode formed by electrostatic spaydeposition (ESD) for an electrochemical energy storage device accordingto the present disclosure includes a plurality of composite particlesadapted for electrostatic deposition onto a conductive current collectorsubstrate. Each composite particle of the plurality of compositeparticles (or at least the vast majority of composite particles)includes an active material particle and binder particles surroundingthe active material particle. Binder particles are formed by eitherbreaking down binder agglomerates into sub particles or directlyintroducing pre-fabricated sub particles. In either case, the binderparticles adhere to a surface of the active material particle throughbonding forces greater than the interaction forces broken duringagitation of the binder agglomerates. Conductive additives may be addedto form the composite.

In FIG. 1 , a range 100 of particles depict an example cathode materialfor an electrochemical energy storage device. In a composite electrodepowder mixture, the active material weight ratio is usually above 80%and the binder and conductive material weight ratio is less than 20% toallow a sufficient gravimetric energy density and acceptable/beneficialpower density for the battery. The composite electrode powder mixture isprepared by a mixing process to allow a uniform dispersion of ingredientparticles. FIG. 1 illustrates several dispersion patterns of particles101A, 101B and 101C of ingredient particles in a well-mixed compositeelectrode powder mixture through dry mixing. Ingredient particlesinclude AM, binder and conductive particles; however in someconfigurations, conductive material is not needed in the compositeelectrode, as will be apparent in the discussion below.

In general, AM particles 111 are the largest, binder particles 112 aresmaller but varied (shown as hatched shaded), and conductive particles113 (shown solid) being of the smallest range. However, in particularimplementations, sizes and size relationships may vary widely. Inparticle 101A, the binder 112 either has a large sub particle size or isin the form of agglomerates. The active material 111 particles keeptheir original morphology during dry mixing. In the static powder form,all particles are well dispersed but there exist no strong interactionsbetween AM 111, binder 112, and CB (conductive) particles 113.

Particle 101B shows that the binder 112 agglomerates are broken in themixing process and the sub particle size is smaller than the activematerial 111. The active material particles keep their originalmorphology during dry mixing. As with 101A, at the static powder form,the particles 111, 112 and 113 may be well dispersed but there exist nostrong interaction forces between AM, binder, and CB particles.

Particle 101C depicts a composite particle where the binder agglomeratesare broken in the mixing process and the sub particle 112 size issmaller than the active material 111. The active material particlesremain in their original morphology during mixing. In the static powderform, binder particles and conductive particles are discretely coated onthe surface of active material particles via surface fusion, Van DerWaal attraction forces, or a variety of potential physical interactionsand chemical bonds. The composite particles 101C are adapted forelectrostatic deposition onto a current collector substrate based on thesub particles of the binder, agitated to break down agglomerates, andthe interaction forces are sufficient to withstand separation forcesinduced from material handling, electrostatic deposition andpost-deposition handling, onto a substrate for maintaining themorphology of the composite particle 101C.

A variety of AM particle and composite particle formulations may beachieved. It should be noted of the distinction between the ingredientparticles of AM, binder and conductive materials, generally obtained asa homogenous bulk granular material, and the formed composite particleformed from particle to particle interaction forces for electrostaticdeposition. In an example arrangement, the active material is formedfrom transition metal oxides for an electrochemical energy storagedevice as cathode material. Typical cathode materials include NCM(Lithium Nickel Cobalt Manganese Oxide), LFP (Lithium Iron Phosphate),LCO (Lithium Cobalt Oxide) or other suitable formulation chemistry,typically based on a form to be able to accept and release lithium ions.Cathode materials may often be formulated from a proprietary process, asopposed to a bulk commodity, prior to deposition. Active material formedfrom the disclosed process may also be anode material for anelectrochemical energy storage device. An exemplary deployment of theactive material is for a rechargeable battery having a chemistry definedby rechargeable lithium batteries, Li-ion batteries, rechargeable Li—Sbatteries, solid state batteries, rechargeable sodium batteries, andsodium-ion batteries. The binder particles are generally formed from oneor more of polymeric materials, polymer electrolytes and solid stateelectrolyte composites; several specific compounds are named above.

FIG. 2 shows a context for deploying the composite particle of FIG. 1 ina battery. An ESD manufacturing process 200 includes an electrostaticdeposition applicator 215, and a hopper 216. The feedstock 214 includesa bulk quantity of composite particles 101C as described above. Thecomposite particles 101C are generated from a mixer 130 having anagitator 132 or similar approach for mixing, combining and adhering thecomposite particles 101C. Sources of bulk particles include activematerial 150-1, binder particles 150-2, and optionally conductiveparticles 150-3 (150 generally). The sources 150 are fed to the mixer130 in predetermined quantities, generally at least 80% weight ratio ofthe active material. The sources 150 result from any suitable commercialor industrial supply, typically as a homogenous bulk stock, and have atexture of a granular, particulate or powder. Particle and powder shouldbe deemed interchangeable in the discussion herein.

Following agitation, the binder particles are usually between 200-1000nm and the conductive particles between 100-500 nm. Once agitated, themixer 130 contains a composite electrode mixture 160 for feedstock 214.AM particles typically range generally from 1-40 μm and aresubstantially larger than the adhered binder and conductive particles,discussed further below.

In an electrostatic deposition apparatus 250 as in FIG. 2 , thecomposite particle of FIG. 1C is depicted as a constituent particle forcathode material. The active material may be either cathode material oranode material, formed from respective cathode material or anodematerial particles. Composite particles from feedstock 214 are aeratedand fluidized by a pressured gas flow, usually dry air. The fluidizedcomposite particles carried by the gas flow pass through theelectrostatic applicator 215 to be charged, travel in the electric fieldand eventually deposit on the grounded conductive current collector 254to form a composite particle layer 252. The composite particlesfluidized and carried by the gas flow are charged by means of coronacharging or tribo charging in the electrostatic applicator 215.

The product output by the electrostatic deposition manufacturing process200 is the coated sheet 253, including the composite particle layer 252and the substrate 254. The electrostatic deposition applicator 215 maybe any suitable electrostatic deposition device. A spray process isoften involved, but other electrostatic deposition approaches may beinvoked. The coated sheet 253 is densified to form the electrode for anelectrochemical energy storage device. The coated sheet 253 can bepre-heated before densification. The densification process can be underheating or without heating. Cathode or anode can be made by the aboveprocess. The densification process may be repeated, e.g., multipletimes. For the electrostatic charging of composite particles, theelectrostatic applicator may employ any suitable electrostatic approach.Electrostatic applications include corona charging, tribo charging,direct electrode induction charging, or other suitable chargingprocesses.

An electrochemical energy storage device, such as Li-ion battery, has acathode, anode, separator and electrolyte. The cathode typicallycomprises active material, such as NCM, binder material, such as PVDF,and conductive material, such as carbon black. The anode typicallycomprises active material, such as graphite, binder material, such asPVDF or SBR/CMC binder, and/or conductive material, such as carbonblack. The separator typically is a porous polymer film, separating thecathode and anode and allowing ion transport between cathode and anode.The electrolyte typically is a lithium salt solution, such as a solutionof LiPF₆ salt and EC/DMC/EMC solvent, which provide ionic conductionbetween the cathode and anode.

In a loading mode, or discharge mode, the anode undergoes oxidation andthe cathode undergoes reduction. In charging, the anode undergoesreduction and the cathode undergoes oxidation. The energy stored in theelectrochemical storage device depends on the electrochemical energystored by the active material, but also the active material content inthe electrode. Furthermore, the uniformity of current distribution inthe electrochemical energy storage device significantly affects thecycle life of the device. The uniformity of current distribution isdirectly related to the uniformity of the electrode. The electrodestructure properties, such as porosity and thickness, affect powercapacity of the electrochemical energy storage device.

Characteristics affected by the formation and layering of the chargematerial include electrode uniformity, active material loading in theelectrode, electrode porosity, electric conductivity, electrodeprocessibility, which are directly related to energy density, powerdensity and cycle life of the resulting battery.

In the electrostatic process 200, the charge of a particle is correlatedto its relative permittivity and size through the following equation:

${q(t)} = {4{{\pi\varepsilon}_{0}\left( {1 + {2\frac{\varepsilon_{r} - 1}{\varepsilon_{r} + 2}}} \right)}r^{2}E\frac{enkt}{{4\varepsilon_{0}} + {enkt}}}$

Where:

r=radius of the particle,

E=electric field strength,

e=charge of an electron,

k=electron mobility,

n=electron concentration,

t=time,

ε₀=absolute permittivity, and

ε_(r)=relative permittivity of powder

The typical particle size range for cathode materials is in the range of1-40 μm. The typical primary particle size of PVDF binder is 200-300 nm.The typical primary particle size of conductive carbon is 40-50 nm. Fromthe above equation, since the maximum charge of the particle is directlyrelated to the square of the particle radius, the charge of theindividual powder constituents during electrostatic deposition will beorders of magnitude different.

The cathode materials usually have much higher relative permittivitythan polymeric binder materials. For example, the relative permittivityof PVDF at 21° C. is about 8-10, and the relative permittivity oflithium nickel oxide-based cathode material is in the order of 1000.

The relaxation time t for charge dissipation from an ideal charged bodyis given by:

τ=ε₀ε_(r)/σ

where:

ε_(r)=relative permittivity of powder and

σ=electronic conductivity of powder

The electronic conductivity of NCM cathode material is generally10⁻⁶-10⁻⁷ S/cm and PVDF <10⁻⁴ S/cm, which results in several ordermagnitude difference in relaxation time for charge dissipation.

Based on the above analysis, due to significant difference inchargeability and charge dissipation time resulting from the differencein conductivity, permittivity, particle size and density, activematerial particles, binder particles and conductive material particleshave different electrostatic deposition behaviors in the electrostaticdeposition process.

Additionally, the differences in particle size, particle density,morphology, surface roughness, and thus surface energy will exhibitdifferent behaviors as they relate to aerodynamic effects during powderfluidization and mechanical conveyance to the coated substrate.

If strong interaction forces do not exist between the particles in themixture, due to the behavioral differences in electrostatic depositionand fluidization associated with powder properties, significantseparation during coating can occur which translates to detrimentaleffects on the coating uniformity regarding the composition,micro-structure and dimension. Conventional approaches, for example,result in a deposition layer 252 having a varied chemical stoichiometryfrom the feedstock 214 due to the different deposition pattern fromindividual ingredient particles.

In the electrostatic deposition process 200, active material particles,binder particles and conductive material particles (formed as in 101Aand 101B) are charged individually when powder particles pass throughthe space charge zone in a corona-charging, tribo-charging, or directplate electrode electrostatic charging systems. Due to the chargeabilityand charge dissipation time differences, individual charged particlesdeposit on the current collector, generating non-uniformities in thedeposited layer.

During formation of the composite particle 101C, the small binderparticles and conductive material particles are attached/adhered on thesurface of active material particles to form composite particles. Duringaeration or mechanical conveyance and deposition of the compositeparticles, consisting of active material particles with surfaceattachment of binder and conductive material particles, the compositeparticles are charged and deposited, which results in a uniformdeposition on the current collector substrate 254. Furthermore, due tothe high resistivity of binder particles 112, a charge dissipation timeof the composite particles is longer than the pure active materialparticles, which enables the electrostatic forces to have an effectduring post coating handling until the curing operation of the bindercan be performed. Thus, the composition of the composite particle 101Cin the feedstock 214 electrode powder mixture is particularly beneficialfor electrostatic deposition to achieve a high degree of uniformity.

FIGS. 3A and 3B show example compositions of the composite particle ofFIG. 1 . Referring to FIGS. 1-3A-3B, FIG. 3A shows the compositeparticle 101C with an AM particle 111 and adhered binder particles 112.FIG. 3B shows that composite particle 101C further includes conductiveparticles 113. Depending on the mixer 130 arrangement, the compositeparticle 101C may be formed from concurrent mixing of the conductiveparticles 113, the active material particles 111 and the binderparticles 112. In an alternate configuration, the composite particle101C further includes combining the conductive particles 113 to adhereto a surface of the binder particles 112, and subsequently forming thecomposite particle 101C by adhering the combined binder and conductiveparticles to a surface of the AM particle 111.

To achieve a composite electrode powder mixture formed of compositeparticles 101C, any mixing/particle coating equipment can be used, suchas impact mixers or shear mixers. The binder agglomerates are brokendown to form sub particles and conductive material agglomerates arebroken down to smaller particles. These sub particles areattached/adhered relative to the surface of active material particlesvia surface fusion, Van Der Waal attraction forces, or a variety ofpotential physical interactions or chemical bonds to produce largeenough interaction forces between the individual particles to form aneffective composite particle which can overcome particle separationduring electrostatic charging, fluidization, mechanical conveyance,and/or deposition processes.

FIG. 4 shows a progression through the formation of the compositeparticle of FIGS. 1-3B. An important feature of the mixing and agitationis to break agglomerates 112′ of binder into sub particles 112, if suchagglomerates exist in the raw material source. Agitation also reducesconductive particles 113′ into smaller sub particles 113 better suitedfor adherence relative to the AM particles 111. Mixing/agitation issufficient to break the interaction forces 401 between agglomerates, andalso adheres the binder 112 relative to the AM particle 111 with bondingforces 402 greater than separation forces experienced through theelectrostatic deposition system 200, maintaining the morphology of thecomposite particle 101C and providing uniform deposition of the layer252.

The sizes shown in FIG. 4 are illustrative and for example purposesonly. In actual production, it is expected that the size of the bindersub particles 112 will range between 0.1%-70% of an average size of theactive material particles 111. It is beneficial if the average subparticle size of binder is less than 10% of the active material when themean particle size of the active material is more than 5 μm. When themean particle size of the active material is less than 5 μm, thepreferred average sub particle size of binder is less than 70% of theactive material.

The granular feedstock 150 can be expected to exhibit variations inparticle sizes, and generally a range in sizes is expected and normal.Rogue particles outside the ranges denoted herein will be unlikely tohave a negative effect, as long as the overall ranges exhibit a typicaldistribution and average. A similar distribution range is tolerable foragglomerates and sub particles as discussed above; not allagglomerates/secondary particles can be expected to always break downwith exacting uniformity.

The sub particle size of the conductive material is 1-100% of theaverage sub particle size of binder. The sub particle size of theconductive material is preferred to be less than 30% of the average subparticle size of binder. From the constituent or ingredient particles,it may be that not all of the binder 112 and conductive particles 113adhere relative to an active material particle 111. In the electrodepowder mixture, more than 50% weight of binder sub particles should beattached relative to the surface of active material particles. It ispreferred that more than 80% weight of binder sub particles are attachedrelative to the surface of active material particles. More than 50%weight of conductive sub particles attach relative to the surface of subparticles of the binder. And more than 50% binder/conductive compositeparticles attach relative to the surface of active material particles.It is preferred that more than 80% weight ratio of the binder andconductive material are attached relative to the surface of activematerial particles.

If the composite electrode mixture does not contain conductivematerial(s), the binder sub particles are directly attached relative tothe surface of active material particles.

The active material powder, binder powder and/or conductive materialpowder can be loaded and mixed in a mixer at the same time. To enablebetter breakage of the binder and conductive agglomerates and anincreased interaction between sub particles of binder and conductivematerial, it is preferred to pre-mix the binder and conductive material,followed by mixing with the active material powder.

Some additional particle stock sizing is as follows. The sub particlesize of the conductive material is 1-100% of the average sub particlesize of binder. The sub particle size of the conductive material ispreferred to be less than 30% of the average sub particle size ofbinder.

In alternate arrangements, methods to attach/adhere binder/conductiveparticles relative to the active material particles are not limited todry powder mixing as described herein. For example, in one exemplaryembodiment, binder/conductive material particles can be coated onto theactive material particles through mixing suspension or solution ofbinder/conductive material with the active material powder. In anotherexemplary embodiment, binder particles can be coated onto/relative tothe surface of active material particles through a spray drying method.

In a particular use case, the mixer 130 employs a high-shear mixer toagitate an NCM/binder/CB powder mixture with standard binder subparticle size for electrostatic deposition. The high-shear mixer offersunique rotating mixing pan with built-in an eccentric mixing tool.Mixing speeds in the range of 1 to 30 m/s can be set to disperse and mixparticles with different sizes. Active material (NCM) with size around10 μm, PVDF binder with a primary size of 200-300 nm, and conductivecarbon with a primary size of 40-50 nm were used in this example.AM/binder/CB particles with 96:2:2 weight ratio was mixed using ahigh-shear mixer for 30 mins. SEM imaging of the mixed particles showscoating of CB and binder on the surface of AM.

Examples

1. Material Preparation and Electrode Preparation with ElectrostaticSpray Deposition

Batches of 700 g powder mixture containing heat treated NMC, PVDF, andcarbon black with a weight ratio of 90:7:3 were loaded into a high-shearmixer. Mixing studies were conducted with different mixing speed andmixing time (Sample 1: 12 m/s, 10 min; Sample 3: 20 m/s, 20 min; Sample4: 25 m/s, 20 min).

The mixed NMC powder was loaded into a hopper in an electrostatic spraydeposition system. The dry powder was fluidized by carrying gas undervibration. The fluidized powder was charged by a corona electrostaticspray gun and deposited on a 15 μm thick grounded Al foil. The coatingside of the Al foil was pre-coated a PVDF interface layer with athickness less than 1 μm applied by electrostatic spray depositiontechnique. The deposited sample was heated in a hotplate for about 1 hrat 250° C. to melt the binder. Finally, the annealed sample was pressedusing a roller press to a desired thickness to achieve 35% porosity.This electrode sample is ready for SEM/EDS, adhesion and electrochemicaltest.

2. SEM/EDS Tests of Samples 1, 3 and 4

The mixed powder samples were analyzed by SEM/EDS to evaluate thedeagglomeration of PVDF/carbon particles and the coating of PVDF/carbonon NMC particles. As shown in FIG. 5A, although few agglomerations ofPVDF/carbon can be seen attaching to the NMC surface, the majority ofthe NMC surface is exposed. The NMC surface texture is clearly visible.This shows that the surface of NMC is barely covered by PVDF/carbonparticles under 12 m/s, 10 min of mixing.

As the mixing intensity increases to 20 m/s, 20 min (Sample 3; FIG. 5B),and 25 m/s, 20 min (Sample 4, FIG. 5C), the surface of NMC particles iscovered entirely by PVDF/carbon.

FIGS. 6A-6C show SEM images of larger areas of the mixed powders forSample 1 (FIG. 6A), Sample 3 (FIG. 6B) and Sample 4 (FIG. 6C).

The corresponding EDS results are shown in FIG. 7A (Sample 1; nickelmapping), FIG. 7B (Sample 3; nickel mapping) and FIG. 7C (Sample 4;nickel mapping), and in FIG. 8A (Sample 1; fluorine mapping), FIG. 8B(Sample 3; fluorine mapping) and FIG. 8C (Sample 4; fluorine mapping).ImageJ was used to process the element mapping images and remove theeffect of signal intensity on image quality. The maximum intensity ofeach element is reported in the image.

As shown in FIGS. 7A-7C, the distribution of nickel can be completelymapped on to the corresponding SEM images. The general shape ofindividual NMC particles is captured by nickel mapping. Mapping offluorine (FIGS. 8A-8C), which is an indication of PVDF content, showsdistinctive differences between the three mixed materials.

The general spherical shape of NMC particles is not visible from thefluorine mapping image of 12 m/s, 10 min mixing (FIG. 8A). Thisindicates that most of the PVDF particles are still randomly placed inthe mixed powder instead of attached to the NMC particles. The tightlygrouped black spots (indicated by arrow) around the bottom left cornerof the image also indicates that some agglomerations of PVDF particlesare not broken under the low intensity mixing.

Fluorine starts to converge to illustrate the spherical shape of NMCparticles with higher intensity mixings, as shown in the 20 m/s, 20 min(Sample 3; FIG. 8B), and 25 m/s, 20 min (Sample 4; FIG. 8C). The tightlygrouped black spots (indicated by arrow) around the center left of thefluorine mapping of the 20 m/s, 20 min mixing (Sample 3; FIG. 8B)indicates a large agglomeration of PVDF particles. Although it isvisible that an NMC particle is behind this large agglomeration of PVDFparticles from the corresponding SEM image in FIG. 6B, the PVDFagglomeration completely blocks the x-ray spectra of nickel of beingcollected by the detector. Therefore, it is shown as a vacancy in thecorresponding nickel mapping image (indicated by arrow). Large PVDFagglomerations are not visible in powder mixed by 25 m/s, 20 min (Sample4). A relatively homogeneous distribution of PVDF particles is achievedand visible from the corresponding fluorine mapping image of FIG. 8C.

3. Adhesion Test

The bonding strength of the electrode was evaluating using a pull-offtest. The electrode sample was cut to a disc with a diameter of 14.3 mm.The electrode disc was attached onto a flathead tip with a diameter of12.7 mm using double-side tape. The disc was attached to a base with adouble-side tape with a 15N compression force, followed by pulling andrecording the maximum pulling force that results in disc collapsing.FIG. 9 is a plot showing bonding strength for electrodes prepared byelectrostatic spray deposition with powders with various mixing time andspeed, i.e., Samples 1, 3 and 4. The plot of FIG. 9 shows the samplesprepared with longer mixing time demonstrated better adhesion.

The disclosed electrochemical energy storage devices may be incorporatedinto various assemblies/sub-assemblies, e.g., a rechargeable lithiumbattery, a Li-ion battery, a rechargeable lithium sulfur battery, asolid state battery, a rechargeable sodium battery, and/or a sodium-ionbattery.

While the system and methods defined herein have been particularly shownand described with references to embodiments thereof, it will beunderstood by those skilled in the art that various changes in form anddetails may be made therein without departing from the scope of theinvention encompassed by the appended claims.

1. An electrode, comprising: a conductive current collector substrate;one or more electrostatic deposited coating layers deposited on theconductive current collector substrate and adhered relative to theconductive current collector substrate; wherein the one or moreelectrostatic deposited coating layers includes a plurality of dry mixedcomposite particles, each dry composite particle of the plurality of drymixed composite particles including (i) one or more active materialparticles, and (ii) deagglomerated binder particles surrounding each ofthe one or more active material particles; and wherein thedeagglomerated binder particles adhere relative to a surface of anactive material particle from among the one or more active materialparticles through interactions that are sufficient to withstand mixingassociated with formation of the dry composite particles and to overcomeseparation forces induced from the depositing of the one or moreelectrostatic deposited coating layers on the conductive currentcollector substrate; thereby maintaining a structure of the compositeparticle when applied onto the conductive current collector substrate.2. The electrode of claim 1, wherein the one or more active materialparticles function as a cathode material.
 3. The electrode of claim 2,wherein the one or more active material particles are selected from (i)lithium transition metal oxides, lithium transition metal sulfides,lithium polyanion cathode materials, including lithium transition metalphosphates, lithium transition metal silicates or their combinations orfrom (ii) sodium transition metal oxide, sodium polyanion cathodematerial, Prussian Blue Analogues cathode materials, or theircombinations.
 4. The electrode of claim 1, wherein the one or moreactive material particles function as an anode material.
 5. Theelectrode of claim 4, wherein the one or more active material particlesare selected from (i) carbonaceous anode materials, graphite, Si,Si-based composites, SiOx, lithium alloyable materials, or lithiumtransition metal oxide anode materials or their combinations, or from(ii) sodium alloyable materials or ion intercalation anode materials,including Prussian Blue Analogues anodes, and sodium metal transitionmetal oxide anodes.
 6. The electrode of claim 1, wherein the structureis incorporated into an assembly selected from the group consisting of arechargeable lithium battery, a Li-ion battery, a rechargeable lithiumsulfur battery, a solid state battery, a rechargeable sodium battery,and a sodium-ion battery.
 7. The electrode of claim 1, wherein thedeagglomerated binder particles are formed from one or more of polymericmaterials, polymer electrolytes and solid state electrolyte composites.8. The electrode of claim 7, wherein the polymeric materials areselected from polyvinylidene fluoride, polytetrafluoroethylene,polyethylene oxide, poly(methyl methacrylate), polystyrene butadienerubber binder, carboxymethyl cellulose binder, polyacrylic acid or acombination thereof.
 9. The electrode of claim 1, wherein the dry mixedcomposite particles further comprise conductive particles adhered to asurface of at least one of the one or more active material particles andthe deagglomerated binder particles.
 10. The electrode of claim 9,wherein the conductive particles are selected from the group consistingof carbon black, carbon nanotube, carbon fiber, graphene, graphite, or acombination thereof.
 11. The electrode of claim 1, wherein theconductive current collector substrate is selected from an Al or Cufoil.
 12. The electrode of claim 11, further comprising a prime layer toenhance adhesion between the one or more electrostatic deposited coatinglayers and the conductive current collector substrate.
 13. The electrodeof claim 1, wherein a size of the deagglomerated binder particles isbetween 0.1%-70% of an average size of the one or more active materialparticles.
 14. The electrode of claim 1, wherein an average size of theone or more active material particles is greater than 5 μm, and anaverage size of the deagglomerated binder particles is less than 10% ofthe average size of the one or more active material particles.
 15. Theelectrode of claim 1, wherein an average size of the one or more activematerial particles is less than 5 μm, and an average size of thedeagglomerated binder particles is less than 70% of the average size ofthe one or more active material particles.
 16. The electrode of claim 1,wherein the dry mixed composite particles further comprise conductiveparticles, and wherein greater than 50% of the deagglomerated binderparticles and the conductive particles are adhered relative to an activematerial particle from among the one or more active material particles.17. A method for forming an electrode, comprising: combining one or moreactive material particles and deagglomerated binder particles to form aplurality of dry mixed composite particles wherein the deagglomeratedbinder particles surround each of the one or more active materialparticles; adhering the plurality of dry mixed composite particlesrelative to a surface of a conductive substrate by an electrostaticdeposition process.
 18. The method of claim 17, further comprising:deagglomerating an agglomeration of binder material to form thedeagglomerated binder particles.
 19. The method of claim 17, furthercomprising: combining conductive particles with the one or more activematerial particles and deagglomerated binder particles, wherein theconductive particles adhere relative to a surface of the deagglomeratedbinder particles, and subsequently forming the composite particles byadhering the combined binder and conductive particles to a surface ofthe one or more active material particles.
 20. The method of claim 17,wherein the electrostatic deposition process is selected from the groupconsisting of corona-charging electrostatic deposition, tribo-chargingelectrostatic deposition and direct electrode induction chargingdeposition.
 21. The method of claim 17, wherein the deagglomeratedbinder particles are formed from binder material by combining the one ormore active material particles and the binder material and agitating adry mixture thereof to overcome agglomeration forces and form thedeagglomerated binder particles from the binder material; therebyadhering the deagglomerated binder particles to a surface of the one ormore active material particles to form composite particles havinginteraction forces between the deagglomerated binder particles and theone or more active material particles sufficient to maintain adherenceduring electrostatic charging, fluidization and mechanical conveyance.22. The method of claim 21, wherein the agitation imparts sufficientforce to pulverize the dry mixture.
 23. The method of claim 21, whereinadherence of the plurality of dry mixed composite particles relative tothe surface of the conductive substrate comprises depositing theplurality of composite particles onto the conductive substrate forforming a coating layer having predetermined active material loading;and further comprising densifying the coating layer and conductivesubstrate through a densification process selected from the groupconsisting of (i) pre-heating the coating layer and conductive substrateprior to the densification process, (ii) pre-heating the coating layerand conductive substrate prior to densification under heating, and (iii)densification of the coating layer and conductive substrate underheating.
 24. The method of claim 23, wherein the densification processis undertaken repeatedly.
 25. The method of claim 21, wherein theagitation results in deagglomerated binder particles sized between200-1000 nm.
 26. The method of claim 17, wherein the combining stepincludes combining conductive particles with the one or more activematerial particles and the deagglomerated binder particles to form theplurality of dry mixed composite particles, whereby the conductiveparticles adhere relative to the deagglomerated binder particles. 27.The method of claim 17, wherein the deagglomerated binder particles areformed from binder material by combining the one or more active materialparticles and the binder material and agitating a dry mixture thereof toovercome agglomeration forces and form the deagglomerated binderparticles from the binder material; wherein a structure of the one ormore active particles is maintained during the agitation and adherencerelative to the surface of the conductive substrate; wherein thedeagglomerated binder particles are formed by dissociating agglomeratesof binder materials; and wherein combination of the one or more activematerial particles and the deagglomerated binder particles to form theplurality of dry mixed composite particles comprises agitating the oneor more active material particles and deagglomerated binder particles ina solventless manner for adhering the deagglomerated binder particlesand maintaining morphology of the one or more active material particlesduring agitation.
 28. The method of claim 17, wherein furthercomprising: combining the deagglomerated binder particles withconductive particles so as to adhere the conductive particles relativeto the deagglomerated binder particles; and adhering the combineddeagglomerated binder particles and conductive particles to a surface ofone of the one or more active material particles to form the dry mixedcomposite particles, wherein the dry mixed composite particles have lessthan 20% by weight of a total of conductive particles and deagglomeratedbinder particles; wherein an average size of the binder particle is lessthan 50% of a mean active material particle size; and wherein an averagesize of the conductive particle is less than 30% of the average size ofthe deagglomerated binder particle.
 29. The method of claim 17, furthercomprising forming an electrode from the conductive substrate withadhered dry mixed composite particles.
 30. The method of claim 17,further comprising including the conductive substrate with adhered drymixed composite particles in a battery.